Science of the Total Environment 408 (2010) 999–1006

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Science of the Total Environment

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / s c i t o t e n v

Review

An evidence-based environmental perspective of manufactured silver nanoparticle in

syntheses and applications: A systematic review and critical appraisal of
peer-reviewed scientific papers
Thabet M. Tolaymat a,⁎, Amro M. El Badawy b, Ash Genaidy c, Kirk G. Scheckel a,
Todd P. Luxton a, Makram Suidan b
a
USEPA Office of Research and Development, National Risk Management Laboratory, 26 West Martin Luther King Drive, Cincinnati, OH 45224, United States
b
Dept. of Civil & Environmental Engineering, University of Cincinnati, Cincinnati, OH, United States
c
WorldTek Inc, Cincinnati, OH, United States

a r t i c l e i n f o a b s t r a c t

Article history: Background: Most recently, renewed interest has arisen in manufactured silver nanomaterials because of
Received 3 April 2009 their unusually enhanced physicochemical properties and biological activities compared to the bulk parent
Received in revised form 20 October 2009 materials. A wide range of applications has emerged in consumer products ranging from disinfecting medical
Accepted 2 November 2009 devices and home appliances to water treatment. Because the hypothesized mechanisms that govern the fate
Available online 27 November 2009
and transport of bulk materials may not directly apply to materials at the nanoscale, there are great concerns
in the regulatory and research communities about potential environmental impacts associated with the use
Keywords:
of silver nanoparticles. In particular, the unlimited combinations of properties emerging from the syntheses
Silver
Nanoparticle
and applications of silver nanoparticles are presenting an urgent need to document the predominant salt
Syntheses precursors, reducing agents and stabilizing agents utilized in the synthesis processes of silver nanoparticles
Evidence–based approach to guide the massive efforts required for environmental risk assessment and management.
Objectives: The primary objective of this study is to present an evidence-based environmental perspective of
silver nanoparticle properties in syntheses and applications. The following specific aims are designed to achieve
the study objective: Aim 1 — to document the salt precursors and agents utilized in synthesizing silver
nanoparticles; Aim 2 — to determine the characteristics of silver nanoparticles currently in use in the scientific
literature when integrated in polymer matrices to form nanocomposites and combined with other metal
nanoparticles to form bimetallic nanoparticles; Aim 3 — to provide a summary of the morphology of silver
nanoparticles; and (4) Aim 4 — to provide an environmental perspective of the evidence presented in Aims 1 to 3.
Methods: A comprehensive electronic search of scientific databases was conducted in support of the study
objectives. Specific inclusion criteria were applied to gather the most pertinent research articles. Data and
information extraction relied on the type of synthesis methods, that is, synthesized silver nanoparticles in general
and specific applications, nanocomposites, and bimetallic techniques. The following items were gathered for:
type of silver salt, solvent, reducing agent, stabilizing agent, size, and type of application/nanocomposite/
bimetallic, and template (for nanocomposites). The description of evidence was presented in tabular format. The
critical appraisal was analyzed in graphical format and discussed.
Results: An analysis of the scientific literature suggests that most synthesis processes produce spherical silver
nanoparticles with less than 20 nm diameter. Silver nanoparticles are often synthesized via reduction of AgNO3,
dissolution in water, and utilization of reductants also acting as capping or stabilizing agents for the control of
particle size to ensure a relatively stable suspension. Two of the most commonly used reductants and stabilizing
agents are NaBH4 and citrate which yield particles with a negative surface charge over the environmental pH
range (3–10). The environmental perspectives of these parameters are discussed.
Concluding remarks: It is expected that the antibacterial property of bulk silver is carried over and perhaps enhanced,
to silver nanoparticles. Therefore, when one examines the environmental issues associated with the manufacture
and use of silver nanoparticle-based products, the antibacterial effects should always be taken into account
particularly at the different stages of the product lifecycle. Currently, there are two arguments in the scientific
literature about the mechanisms of antimicrobial properties of silver nanoparticles as they relate to colloidal silver
particles and inonic silver. Methodologies of risk assessment and control have to account for both arguments.
Published by Elsevier B.V.

⁎ Corresponding author. Tel.: +1 513 487 2860; fax: +1 513 569 7879.
E-mail address: [email protected] (T.M. Tolaymat).

0048-9697/$ – see front matter. Published by Elsevier B.V.

doi:10.1016/j.scitotenv.2009.11.003
1000 T.M. Tolaymat et al. / Science of the Total Environment 408 (2010) 999–1006

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1000
2. Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
2.1. Search strategy and inclusion criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
2.2. Data/information extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
2.3. Data collection, management and analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
3. Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
3.1. Identification of studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
3.2. Description of evidence and critical appraisal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
3.2.1. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
3.2.2. Nanocomposites and bimetallic nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
3.2.3. Particle morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
3.3. Synopsis of silver nanoparticle applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
4. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1004
5. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005

1. Introduction agents, if warranted, to prevent agglomeration of nanoparticles.

Indeed, the solvents and reducing agents used in these processes
Historically, silver compounds and ions have been extensively affect the physical and morphological characteristics of manufactured
used for both hygienic and healing purposes (Chen and Schluesener, silver nanoparticles. In turn, these specific characteristics will
2008). However, over time, the use of silver compounds and ions has influence the fate, transport and toxicity of nanoparticles in the
faded as an anti-infection agent due to the advent of antibiotics and environment. For example, the use of sodium citrate as a reducing
other disinfectants and the poorly understood mechanisms of their agent generates a negatively charged silver nanoparticle which may
toxic effects. Most recently, renewed interest has arisen in manufac- behave differently than a positively charged silver nanoparticle
tured silver nanomaterials because of their unusually enhanced generated via branched polyethyleneimine (BPEI) (Tan et al., 2007).
physicochemical and biological properties activities compared to the Intermediates or by-products are often generated in these techniques,
bulk parent materials. A wide range of applications has emerged in thereby playing a critical role in nanoparticle synthesis. Furthermore,
consumer products ranging from disinfecting medical devices and the incorporation of silver nanoparticles in nanocomposites and
home appliances to water treatment (Li et al., 2008a,b). bimetallic nanoparticles may augment environmental concerns due to
Because the hypothesized mechanisms that govern the fate and the uncertainty surrounding the inclusion of another metal or poly-
transport of bulk materials may not directly apply to materials at the mer, possibly increasing nanoparticle toxicity.
nanoscale, there are great concerns in the regulatory and research In light of the above, one can realize the unlimited combinations of
communities about the potential environmental impacts associated properties and substances involved in the syntheses and applications
with the manufacture and use of silver nanoparticles. This research of silver nanoparticles. Consequently, there is an urgent need to
provides an evidence-based environmental perspective of the sub- document the predominant salt precursors, reducing agents and
stances used in synthesizing silver nanoparticles as well as their stabilizing agents utilized in the synthesis processes of silver
properties, thus, leading to focused attention to the most appropriate nanoparticles to guide the massive efforts required for environmental
steps to be taken in environmental risk assessment and control risk assessment and management.
throughout the product lifecycle. Until more detailed findings emerge The primary objective of this study is to present an evidence-based
from toxicological studies, the evidence provided in this research can environmental perspective of silver nanoparticle properties in
assist, among other things, in developing relative risk analyses. Such syntheses and applications. The following specific aims are designed
approach was recently adopted to evaluate the relative risk of to achieve the study objective: Aim 1 — to document the salt
manufactured nanomaterials. A representative synthesis method precursors and agents utilized in synthesizing silver nanoparticles;
was selected by Robichaud et al. (2005) for a given manufactured Aim 2 — to determine the characteristics of silver nanoparticles
nanomaterial based on its potential for scale-up. A list of input and currently in use in the scientific literature when integrated in polymer
output materials and waste streams for each step of fabrication was matrices to form nanocomposites and combined with other metal nano-
developed and entered into a database that included key process particles to form bimetallic nanoparticles; Aim 3 — to provide a
characteristics. The physical–chemical properties and quantities of summary of the morphology of silver nanoparticles; and (4) Aim 4 — to
inventoried materials were used to qualitatively assess the risks based provide an environmental perspective of the evidence presented in
on factors such as volatility, carcinogenicity, flammability, toxicity, Aims 1 to 3.
and persistence. The work presented herein supplements but do not duplicate
In general, silver nanoparticles are synthesized using various earlier reviews on the subject (Boxall et al., 2007; Luoma, 2008; Blaser
techniques resulting in different shapes and sizes for use in numerous et al., 2008; Mueller and Nowack, 2008). Boxall et al. (2007)
applications. The synthesis techniques are categorized into top-down developed a range of models aiming at predicting the concentrations
and bottom-up approaches (del Rocío Balaguera-Gelves, 2006). The of a wide variety of engineered nanoparticles in water and soils.
top-down techniques use silver metal in its bulk form, then, Luoma (2008) presented an overview of silver and the environment
mechanically reduce its size to the nanoscale via specialized including the expected quantities to be released, sources of release,
methodologies such as lithography and laser ablation (Amendola expected pathways, and toxicity. Blaser et al. (2008) modeled
et al., 2007). The bottom-up (also known as self-assembly) technique environmental concentrations of silver and demonstrated that, by
involves the dissolution of silver salt into a solvent and the subsequent 2010, nanosilver in plastics and textiles are expected to contribute up
addition of a reducing agent, with the supplemental use of stabilizing to 15% to the total silver released into water in the European Union.
 T.M. Tolaymat et al. / Science of the Total Environment 408 (2010) 999–1006 1001

Similarly, Mueller and Nowack (2008) presented the results of 3.2.1. Synthesis
modeling environmental concentrations of nanoparticles including Analysis of the reviewed articles suggests that the bottom-up
nanosilver. technique was predominantly used in the synthesis of silver
nanoparticles relative to the top-down technique (b4% of reviewed
2. Methods articles). This is mainly attributed to the surface imperfection of
formed particles used in the top-down approach, thereby, impacting
2.1. Search strategy and inclusion criteria their applicability (Kildeby et al., 2005). Consequently, the description
of evidence presented in Tables S1 and S2 is based on the bottom-up
The electronic search was initially conducted on the ‘Scopus’ synthesis techniques. An analysis of the evidence is presented
database with the following keywords: silver, nanoparticles, synthe- separately by metal salt precursor, solvents, and reducing and
sis. To further refine the search, the following inclusion criteria were stabilizing agents.
adopted: general applications, specific applications, nanocomposites,
and bimetallic. In addition to Scopus, general search engines such as 3.2.1.1. Metal salt precursor. Silver salt precursors are used in bottom-
Google and Yahoo were used. The bibliographies of retrieved articles up techniques to produce ionic silver, which can be reduced and
were also searched for pertinent references not included in the precipitated to form nanoparticles. Fig. 1 suggests that silver nitrate
electronic search. Only reports and papers published in English were (AgNO3) is the most widely used salt precursor accounting for almost
used, with the electronic search conducted in August of 2008. 83% of those reported in studies of general and specific synthesis
methods. The dominant use of AgNO3 is attributed to its low cost and
2.2. Data/information extraction chemical stability when compared to other types of silver salts (Lee
et al., 2007). Thus, although it is likely that nitrate will be the
Data and information extraction relied on the type of synthesis dominant anion associated with the production of silver nanoparti-
methods. The following items were gathered for synthesized silver cles, nitrate is a reaction/synthesis byproduct that is classified by the
nanoparticles in general applications: type of silver salt, solvent, United States Environmental Protection Agency (US EPA) as a primary
reducing agent, stabilizing agent, and size. Specific applications drinking water contaminant (MCL = 10 mg L− 1). In light of the above,
featured the following items for synthesized silver nanoparticles: it is logical to assume that an environmental release from a manu-
type of application, silver salt, solvent, size as well as reducing facturing facility will be concerned with not only silver nanoparticles
and stabilizing agents. Similar data and information were assem- but also nitrate.
bled for silver nanocomposites and bimetallic with the addi-
tional items of type of nanocomposite or bimetal and template for 3.2.1.2. Solvents. Solvents are used to solubilize silver salts and other
nanocomposites. chemicals included in the synthesis processes. Although organic and
inorganic solvents are used in synthesizing silver nanomaterials,
2.3. Data collection, management and analysis approximately 80% of synthesis processes use water as a solvent in the
reported studies (Fig. 2). A good share of organic solvents is
The description of evidence was presented separately in tabular particularly used in the production of relatively high particle
format for general synthesis applications, specialized synthesis concentrations coupled with predefined shapes and sizes (e.g.:
methods, nanocomposite and bimetallic forms. In addition, a critical Dorjnamjin et al., 2008; Yang et al., 2005). Thus, the emergence of
appraisal of those general classifications was graphically displayed organic solvents in scalable synthesis processes raises concerns for
and presented in terms of the type of salt, solvents, reducing agents, their environmental impacts in comparison to the low environmental
stabilizing agents and particle size used in the synthesis methods. An impact of water. One can deduce from the use of water as a solvent
environmental perspective of each of those items was presented. that most processes yield potentially stable and mobile silver
nanoparticles in an aqueous environment. Although research is
3. Results lacking in the area of silver nanoparticle transport, the potential for
transport into and via surface and ground water may be greater than
3.1. Identification of studies

The general electronic search yielded 18,793 articles from the

Scopus database. A subsequent focused search was followed with the
previously stated inclusion criteria. About 400 articles were deemed
relevant to the reported research. All abstracts were reviewed for
relevance and only needed articles were obtained. The final electronic
and manual search resulted in nearly 200 research articles for use in
this study.

3.2. Description of evidence and critical appraisal

From an environmental perspective, the description of evidence

was presented separately in tabular format for synthesized silver
nanoparticles for general applications (see Supplementary informa-
tion: Table S1), synthesized silver nanoparticles for specific applica-
tions (Supplementary information: Table S2), silver nanocomposites
(Supplementary information: Table S3), and bimetallic nanoparticles
(Supplementary information: Table S4). Table S5 includes the details
of acronyms listed in Tables S1 to S4, respectively of Supplementary
information. The details of description of evidence and critical
appraisal for the reviewed articles are presented in the following Fig. 1. Analysis of silver salt precursors reported in studies of silver nanoparticle
sections. synthesis.
1002 T.M. Tolaymat et al. / Science of the Total Environment 408 (2010) 999–1006

with borides (Bönnemann et al., 1994, Sardar et al., 2007). For

example, Bönnemann et al. (1994) reported that the reduction of
nickel choride with sodium borohydride results in a nickel powder
with 5% boron.

3.2.1.4. Stabilizing agents. A stabilizing agent (also known as capping

agent) is used in the synthesis process to prevent nanoparticles from
aggregation and to control the size of final product, with agglomera-
tion mainly caused by excess surface energy and high thermodynamic
instability of the nanoparticle surface (Olenin et al., 2008). A
stabilizing agent relies on electrostatic repulsion force caused by
surface charge, steric stabilization, or both (Guo et al., 2008; Sun and
Luo, 2005; Hasell et al., 2007). Consequently, there is a wide selection
of stabilizing agents to choose from as shown in Fig. 4 including
surfactants such as sodium dodecyl sulfate (SDS) or ligands and poly-
mers that contain functional groups such as thiol (–SH), cyano (–CN),
carboxyl (–COOH) and amino (–NH2) acting as stabilizers (Olenin
et al., 2008; Si and Mandal, 2007).
The selection of stabilizing agent depends on the application. For
example, polynisopropylacrylamide (PNIPAM) is commonly used as a
Fig. 2. Analysis of solvents reported in studies of silver nanoparticle synthesis. temperature-sensitive polymer possessing a lower critical solution
temperature (LCST). Below the LCST, it is hydrophilic and soluble in
previously thought in the event of these particles forming stable sus- aqueous solution; however, the polymer becomes hydrophobic,
pensions in water. insoluble and aggregates in solution when the temperature is raised
above the LCST. Thus, silver nanoparticles capped by PNIPAM allow
3.2.1.3. Reducing agents. In the context of the bottom-up methodology, for combined surface plasmon and thermal switching applications
a reducing agent is a chemical agent, plant extract, biological agent, or (Guo et al., 2008).
irradiation method that provides the free electrons needed to reduce In addition to the above, the stability, reactivity, solubility, particle
silver ions and to form silver nanoparticles. Although a strong shape and size are determined by the concentration of a given type of
reducing agent such as sodium borohydride (NaBH4) tends to produce a stabilizing agent (Balan et al., 2007). For instance, smaller particles
a narrow range of small monodispersed particles, a weaker reducing are obtained by increasing the carboxylate stabilizer concentration
agent such as ascorbic acid produces larger particle sizes (Chen et al., (Wang et al., 1999). The catalytic properties of silver nanomaterials
2007a). A critical appraisal of the scientific literature embodied in the can also depend on the type of stabilizers used (e.g., cetyltrimethy-
peer-reviewed articles suggests that NaBH4 (∼ 23%) and sodium lammonium bromide (CTAB), SDS), hence, decreasing the adsorption
citrate (∼10%) accounted for 33% of all the used reducing agents of reactants to the silver surface (Jiang et al., 2005). The commonly
(Fig. 3). Smaller percentages of other reducing agents were used in used synthesis methods usually produce negatively charged silver
special synthesis applications. It should be noted that the “other” nanoparticles; however, the use of branched polyethyleneimine
category refers to reducing agents mentioned only one time in the (BPEI) results in positively charged silver nanoparticles that show
reviewed literature and did not fall under any of the specified greater surface enhanced Raman scattering (SERS) activity over
categories. From an environmental perspective, although sodium negatively charged silver nanoparticles (reduced via citrate) for the
citrate may not pose an immediate environmental threat as a reducing detection of thiocyanate and perchlorate ions.
agent, NaBH4 may lead to contamination due to the hydrogen atoms As demonstrated in Fig. 4, an appraisal of the scientific literature
in the BH− 4 anion. In essence, the four hydrogen atoms participate in revealed that sodium citrate (27%) was the most commonly used
the reduction process leaving a surface particle that is contaminated stabilizing agent, followed by polyvinyl pyrrolidone (PVP) (18%), then

Fig. 3. Analysis of reducing agents reported in studies of silver nanoparticle synthesis. Fig. 4. Analysis of stabilizing agents reported in studies of silver nanoparticle synthesis.
 T.M. Tolaymat et al. / Science of the Total Environment 408 (2010) 999–1006 1003

amines (8%). Cetyltrimethylammonium bromide (CTAB), polyvinyl particles). In particular, the optimum combination of these properties
alcohol (PVA), sugars and amides accounted each for 5% of the is obtained for particles in the range of 3 to 10 nm (Olenin et al., 2008).
stabilizing agents used in the reviewed literature. The “other” This is attributed to the high ‘surface area to volume’ ratio and the
category in Fig. 4 represents 23% of all stabilizing agents with quantum confinement effect caused by extremely reduced size (i.e.,
individual chemicals being used in only one article. It should be noted electron confinement in a small area) (Morones and Frey, 2007).
that sodium citrate was used in 50% of the stabilizing agents used in It has been shown that silver nanoparticles with 15 nm diameters
specific applications, followed by PVP (18%), then CTAB/amines/ had the highest toxic effect on rats' alveolar macrophages in
amides/fatty acids with each representing less than 10% of used comparison to larger nanoparticles (i.e., 30 to 55 nm) (Cataleya,
agents. Indeed, one cannot overlook the crucial role of surface 2006). This trend is most likely the result of increased surface reactive
charging properties of silver nanomaterials in affecting their potential area of silver nanoparticles and the comparable size of particle to
mobility and behavior in the environment. Therefore, an assessment protein in biological cells. Silver nanoparticles with 1–10 nm size
of the chemical properties of commonly used stabilizing agents is demonstrated interaction with HIV by inhibiting the virus from
warranted. binding to the host cells (Navaladian et al., 2008). Smaller particle size
does not always translate to an enhancement in the particle
3.2.2. Nanocomposites and bimetallic nanoparticles properties. For example, an SERS application shows enhanced signals
A combination of useful properties such as optical/catalytic/ with larger particle sizes (Dong et al., 2007).
conductive is achieved when silver nanoparticles are integrated into The size can have an effect on the thermodynamic properties of
polymer matrices to form nanocomposites or when they are silver nanoparticles, most notably due to the low ‘surface area to
combined with other metal nanoparticles acting as a shell or a core volume’ ratio which seems to control these properties (Luo et al.,
to form bimetallic nanoparticles (Koh et al., 2008; Dong et al., 2008). 2008). In general, the thermodynamic properties of silver nanopar-
For example, the antibacterial activity of silver nanoparticles was ticles (e.g., melting point and molar heat of fusion) are directly
enhanced when it was incorporated into an Ag/TiO2 nanocomposite proportional to particle diameter (Luo et al., 2008). For example, silver
(Nino-Martınez et al., 2008). The successful catalytic reduction of nanoparticles of less than 10 nm in diameter are utilized in the
specific dyes may be achieved via use of silver nanoparticles semiconductor industry and printed electronic products due to their
supported on silica spheres (Jiang et al., 2005). Furthermore, silver lower melting point (Kashiwagi et al., 2006).
is often used as a substrate for magnifying the SERS providing stronger Silver nanoparticles can be synthesized as 1-D objects (e.g., thin
spectrum than data obtained from using each individual nanoparticle films), 2-D objects (e.g., nanowires, nanorods) and 3-D objects (e.g.,
(Pande et al., 2007). spheres) (Muraviev, 2005). Although nanosilver is synthesized in
An account of the substances used in synthesizing silver various shapes, silver spheres are the dominant shape accounting for
nanocomposites and bimetallic nanoparticles as well as particle approximately 90% of those used in the bottom-up methods. With this
sizes is provided in Tables S3 and S4, respectively. Other materials in mind, one cannot overlook other shapes. Triangular silver
incorporated with silver include multi-walled carbon nanotubes and nanoparticles, for example, had stronger biocidal action against
metallic nanoparticles (Sn, Ru and Pd). As can be observed, the gram-negative bacterium Escherichia coli than spherical and rod-
integration of silver into nanocomposites and bimetallic nanoparticles shaped nanoparticles. This was mainly attributed to the arrangement
is limitless. With each combination, silver is being used to generate of atoms in the crystal structure (Pal et al., 2007).
nanoparticles with new characteristics. Consequently, the environ-
mental impact of nanocomposites and bimetallic nanoparticles has to 3.3. Synopsis of silver nanoparticle applications
be examined on a case-by-case basis. For example, the enhanced
antibacterial effect of Ag/TiO2 may be evidence of higher toxicity The scientific literature points to the wide use of silver in nume-
levels in the ecosystem in the event of release to the environment, rous applications. It is well established that silver nanoparticles are
thus requiring further investigation. known for their strong antibacterial effects for a wide array of
organisms (e.g., viruses, bacteria, fungi) (Wen et al., 2007). Therefore,
3.2.3. Particle morphology silver nanoparticles are widely used in medical devices and supplies
As shown in Fig. 5, the dominant size of silver nanoparticles ranges such as wound dressings, scaffold, skin donation, recipient sites,
from 1 to 10 nm in general applications (approximately 45.5%), with sterilized materials in hospitals, medical catheters, contraceptive
the same trend demonstrated for specific applications (51% of the devices, surgical instruments, bone prostheses, artificial teeth, and
bone coating. One can also observe their wide use in consumer
products such as cosmetics, lotions, creams, toothpastes, laundry
detergents, soaps, surface cleaners, room sprays, toys, antimicrobial
paints, home appliances (e.g., washing machines, air and water
filters), automotive upholstery, shoe insoles, brooms, food storage
containers, and textiles (Amendola et al., 2007; Navaladian et al.,
2008; Fernandez et al., 2008; Thomas et al., 2007).
Other unique properties of silver nanoparticles include their
utilization in fluorescence and surface plasmon resonance (SPR). For
example, SPR occurs upon irradiating silver nanoparticles with visible
light, which then causes the oscillation of free electrons in the
conduction band of nanoparticles. The width and position of SPR peak
depend mainly on the particle size and shape (Basavaraja et al., 2008;
Jiang et al., 2007). These properties allow silver nanoparticles to be
used in sensing applications such as detection of DNA sequences
(Jacob et al., 2008), laser desorption/ionization mass spectrometry of
peptides (Hua et al., 2007), colorimetric sensor for histidine (Xiong
et al., 2008), determination of fibrinogens in human plasma (ZhiLiang
et al., 2007), real-time probing of membrane transport in living
Fig. 5. Particle size (nm) reported in studies of synthesized silver nanoparticles. microbial cells (Xu et al., 2004), enhanced IR absorption spectroscopy
1004 T.M. Tolaymat et al. / Science of the Total Environment 408 (2010) 999–1006

(Huo et al., 2006), colorimetric sensors for measuring ammonia (provided by NanoSys GmbH, Switzerland) to assess the toxicity of
concentration (Dubas and Pimpan, 2008a), biolabeling, optical silver nanoparticles to chlamydomonas reinhardtii. The information
imaging of cancer (Wiley et al., 2007), biosensors for detection of was not presented in this systematic review because the synthesis
herbicides (Dubas and Pimpan, 2008b), and glucose sensor for reactants and methods were not disclosed in the Navarro paper.
medical diagnostics (Mishra et al., 2007). Furthermore, SERS analysis A possible explanation for the lack of such information can be that
techniques can be used to examine trace analysis of pesticides, the innovative methods developed by the nano-manufacturing
anthrax, prostate-specific antigen glucose, nuclear waste, identifica- enterprises are considered as proprietary information. Based on our
tion of bacteria, genetic diagnostics, detection of nitro-explosives own experience, we asked a supplier of silver nanomaterial utilized in
(Marcia, 2006), and immunoassay labeling (Morones and Frey, 2007). various experiments in our laboratory about certain details of the
Electronic applications span the preparation of active waveguides synthesis methods, however, the manufacturer was not willing to
in optical devices, inks for printed circuit boards, optoelectronics, share the information with us. We made another attempt to search
nanoelectronics (e.g., single-electron transistors, electrical connects), electronic databases documenting patents. Our earlier observation
sub-wavelength optics, data storage devices, nonlinear optics, high about the lack of some details in the reporting of synthesis methods
density recording devices, battery-based intercalation materials, can be demonstrated from examination of Table 1. It should be,
provision of micro-interconnects in integrated circuits (IC) and therefore, be kept in mind that the systematic review reported herein
integral capacitors (Navaladian et al., 2008; Kim et al., 2007; only includes synthesis methods that are available to the general
Deshmukh and Composto, 2007). In addition, the large surface area public for review and may not reflect the universe of all synthesis
of silver nanoparticles provides high surface energy, which promotes processes currently in use.
surface reactivity (e.g., adsorption, catalysis). For example, silver On the basis of evidence extracted from the scientific literature, it
nanoparticles and silver nanocomposites have been used to catalyze is clear that silver nanoparticles have unique properties allowing
many reactions such as CO oxidation (Liu et al., 2005), benzene them to be one of the most commonly used nanoparticles in consumer
oxidation for phenol (Ameen et al., 2007), photodegradation of products. Thus, they may eventually reach the environment at
gaseous acetaldehyde (Hamal and Klabunde, 2007), and reduction of different stages of the product lifecycle, that is, manufacturing, con-
p-nitrophenol to p-aminophenol (Fernandez et al., 2008). sumer use, and/or end-of-life management. The body of knowledge
suggests that most synthesis processes produce silver nanoparticles
4. Discussion that are spherical with a diameter of less than 20 nm. Silver
nanoparticles are often synthesized using AgNO3, dissolved in water
An examination of silver nanomaterial synthesis is warranted for with NaBH4 or citrate as a capping agent, which gives these particles a
two primary reasons. First, it allows the identification of dominant negative surface charge. Thus, there is a need to evaluate the effect of
silver nanomaterials currently in use to allow a focused approach in particle-specific factors (e.g., shape and size) and environmental
evaluating their environmental impacts as well as the substances used factors (e.g., pH, ORP) on the fate, mobility and toxicity of silver
in their synthesis. Second, the great majority of synthesis processes nanoparticles, fueling the need for new methodologies as silver
are not environmentally friendly, with only 24% of the reported nanoparticles may behave differently from bulk silver. One point to
methods relying on green or environmentally-friendly techniques. keep in mind is that the conversion of silver ions into silver
This is expected since non-green methods provide more control over nanoparticles is not always 100%. Therefore, one should be cautioned
the reaction process and produce monodisperse silver nanoparticles about the environmental release of those ions that do not make it into
with peculiar characteristics. According to Sharma et al. (2009), green the final silver nanoparticle-based product. According to synthesis
synthetic methods include mixed-valence polyoxometallates, poly- methods in our lab, the point of release may reach up to 30%.
saccharides, tollens, irradiation, and biological; on the other hand, In general, the fate and transport of silver nanoparticles are
conventional or non-green methods involve chemical agents associa- governed by many variables such as capping agent, particle size, and
ted with environmental toxicity. As can be seen from Tables S1 and S2, surrounding environmental conditions (Wiesner et al., 2006).
the green approaches generate large particle sizes. It can also be Furthermore, silver nanoparticles have a surface charge. Since citrate
inferred that particle sizes less than 20 nm are considered the most and PVP are the dominant capping agents, the surface charge of
reactive and are seldom generated using green synthesis methods. nanoparticles will be mainly negative under typical environmental pH
A specific aim of the evidence-based methodology employed in range (4–9). Particle charge will have a profound impact on its
this research was to extract the information from the scientific mobility in the environment. For example, transport through a
literature embodied in peer-reviewed papers (as obtained from negatively charged sandy soil will be dominated by repulsion forces,
electronic scientific databases). We did not take into account other thus, causing silver nanoparticles to be more mobile. Conversely,
evidence which may be present in industrial enterprises. Although transport through positively charged soils will be dominated by
this issue can be regarded as a serious limitation in the present study, attraction forces, thus, hindering silver nanoparticles from reaching
we have attempted to consult general purpose databases such as groundwater. In this latter case, silver nanomaterial may pose a
Google to gather additional evidence for potential inclusion in the hazard to soil organisms that play a vital role in maintaining natural
supplementary information. We found a lack of information which processes.
cannot be presented in the reported supplementary information. For Silver nanoparticles have a reactive surface that is evident by their
example, Navarro et al. (2008) used carbonate-coated nanoparticles usage as substrates to adsorb a variety of analytes for study by SERS. In

Table 1
Samples of work reported in patent electronic database.

Ag salt Reducing agent Solvent Stabilizing agent Size (nm) Source Notes

nr Hydrazine Organic solvent nr nr Li et al. (2008a,b) –

nr Organic solvent Water nr nr Liu (2007) –
nr Polycyclic hydrocarbon/carboxyl acids nr nr nr Nakamoto et al. (2007) –
nr Probiotic bacteria nr nr nr De et al. (2008) –
AgNO3 Ferrous sulfate Water Sodium citrate 20 Uno and Sato (2006) Spherical
AgNO3 Formalin Water nr 1–20 Fujieda and Nishihara (2006) Spherical

Note: ‘nr’ — not reported.

 T.M. Tolaymat et al. / Science of the Total Environment 408 (2010) 999–1006 1005

fact, a number of SERS studies reported the adsorption of 1,2,3-triazole systems that rely heavily on microbial decomposition for treatment
(Pergolese et al., 2004), organo-sulfur compounds and benzyl phenyl (landfills and wastewater treatment plants). Indeed, nano-silver
sulfide (BPS) (Kim et al., 2004), organo-sulfur compounds and benzyl toxicity to aerobic and anaerobic microorganisms should be an
phenyl sulfide (BPS) (Kim et al., 2004), carbonyl species Cr(CO)4dpp integral part of this evaluation. It is equally warranted that the
(Tan et al., 2005,), and cationic dyes (e.g., acridine, 9-aminoacridine and accumulation of silver nanoparticle in biosolids and their effects on
Nile Blue) (Xingcan et al., 2003) in silver nanoparticles. Additionally, management practices of these materials should be investigated.
SO2 (i.e., a pollutant gas) was adsorbed in silver nanoparticles sur-
face causing their agglomeration and settlement from the solution 5. Concluding remarks
(Patakfalvi et al., 2008). It should be noted that silver nanoparticles can
potentially absorb some contaminants from wastewater and convey It is expected that the antibacterial property of bulk silver is carried
them to surface water via the final treated effluent. One can be equally over to and perhaps enhanced in silver nanoparticles. Therefore, when
concerned about the presence of silver in wastewater streams because it one examines the environmental issues associated with the manu-
can impact the microorganisms treating wastewaters. facture and use of silver nanoparticle-based products, the antibac-
It is expected that the antibacterial property of bulk silver is carried terial effects should always be taken into account particularly at the
over to and perhaps enhanced in silver nanoparticles. Therefore, when different stages of the product lifecycle. Currently, there are two
one examines the environmental issues associated with the manu- arguments in the scientific literature about the mechanisms of
facture and use of product-based silver nanoparticles, the antibac- antimicrobial properties of silver nanoparticles as they relate to
terial effects should always be taken into account, particularly at the colloidal silver particles and inonic silver. Methodologies of risk
different stages of product lifecycle depending on the environmental assessment and control have to account for both arguments.
release in the form of colloidal silver particles or silver ions. Different
mechanisms have been proposed for the antimicrobial properties of Acknowledgments
silver nanoparticles: (a) adhesion of nanoparticles to the surface
altering the membrane properties, with possible degradation of This research was funded by the National Risk Management
lipopolysaccharide molecules, accumulation inside the membrane Research Laboratory of the U.S. Environmental Protection Agency
via forming pits and causing large increases in membrane permeabi- Office of Research and Development. The paper has not been
lity; (b) penetration of silver nanoparticles inside the bacterial cell subjected to the Agency's internal review; therefore, the opinions
resulting in DNA damage; and (c) dissolution of silver nanoparticles expressed are those of the authors and do not necessarily reflect the
with releases of antimicrobial ionic silver (Li et al., 2008a,b). official positions and policies of the USEPA.
The above mechanisms suggest that the impact of environmental
releases throughout the product lifecycle seems to take place in the
Appendix A. Supplementary data
form of colloidal silver particles or ionic silver. Contrary to the
bactericideal effects of ionic silver, the antimicrobial activity of
Supplementary data associated with this article can be found, in
colloidal silver particles is influenced by the dimensions of the
the online version, at doi:10.1016/j.scitotenv.2009.11.003.
particles; the smaller the particles, the greater the antimicrobial effect
(Guzman et al., 2008). Silver nanoparticles may attach to the surface
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